CN111111663A - Spherical nano magnetite heterogeneous Fenton catalyst and preparation method and application thereof - Google Patents
Spherical nano magnetite heterogeneous Fenton catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims description 75
- 230000008569 process Effects 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 229910001868 water Inorganic materials 0.000 claims description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 12
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 12
- 239000007822 coupling agent Substances 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 238000002604 ultrasonography Methods 0.000 claims description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 7
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 7
- 238000007885 magnetic separation Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 229960002089 ferrous chloride Drugs 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 239000000149 chemical water pollutant Substances 0.000 claims description 3
- 239000010842 industrial wastewater Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229940113116 polyethylene glycol 1000 Drugs 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 4
- 238000004043 dyeing Methods 0.000 abstract description 3
- 230000005307 ferromagnetism Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000007639 printing Methods 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 description 13
- 239000002253 acid Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 230000033228 biological regulation Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000005291 magnetic effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005294 ferromagnetic effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 229910009112 xH2O Inorganic materials 0.000 description 2
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000006148 magnetic separator Substances 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- 238000001000 micrograph Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Images
Classifications
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- B01J35/40—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/33—
-
- B01J35/51—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention discloses a spherical nano magnetite heterogeneous Fenton catalyst and a preparation method and application thereof. The nano magnetite heterogeneous Fenton catalyst is synthesized by a microwave-assisted hydrothermal method, the prepared catalyst has high catalytic activity, is suitable for being used in a range from weak acidity to neutrality, has ferromagnetism and can be reused, the catalyst loss is avoided, secondary pollution is reduced, and the catalyst has a wide application prospect in the fields of pretreatment and advanced treatment of typical refractory organic wastewater such as papermaking wastewater, printing and dyeing wastewater, tanning wastewater, chemical wastewater, garbage leachate and the like. Meanwhile, the preparation process is simple, the cost is low, and the large-scale production is easy.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method of a heterogeneous Fenton catalyst, in particular to a preparation method of a Fenton catalyst, a Fenton catalyst prepared by the method, and further relates to application of the heterogeneous Fenton catalyst, so that pretreatment or advanced treatment of industrial wastewater and landfill leachate which are difficult to biodegrade is realized.
Background
Advanced Oxidation Processes (AOPs) are processes for generating hydroxyl radicals (. OH), sulfuric radicals (SO) having strong oxidizing power4 ·-) The method is characterized in that physical fields such as high temperature and high pressure, electricity, sound, light and the like or homogeneous and heterogeneous catalysts and the like are used as auxiliary materials, so that macromolecular refractory organic matters are oxidized into low-toxicity or non-toxic micromolecular substances and then degraded into water and carbon dioxide. The advanced oxidation process includes a Fenton process (Fenton), a catalytic ozone process, a photocatalytic process, an electrochemical process, an ultrasonic process, a wet oxidation process, a microwave oxidation process, a radiation oxidation process, and the like.
Fenton process and ozoneThe process is the most mature advanced oxidation technology in industrialization at present, but the Fenton process has strict requirements on the pH value of wastewater, the pH value needs to be 3.0-4.0, and the reaction rate is very low under a neutral condition; secondly, the chroma problem of the effluent is easily caused due to the loss of Fe (III), and thirdly, a large amount of chemical sludge is easily generated in the reaction, thereby causing secondary pollution or increasing the subsequent treatment cost. In recent years, the development of heterogeneous fenton catalysts for replacing fe (ii) has received increasing attention. The catalyst has catalytic efficiency similar to that of Fe (II), can efficiently catalyze hydrogen peroxide to generate OH, can realize separation of the catalyst and reaction liquid through magnetic separation, filtration and the like after reaction is finished, realizes efficient recovery and cyclic utilization of the catalyst, and reduces effluent chromaticity and iron secondary pollution. On the other hand, considering that Fe (II) can exist in an ionic state under a stricter pH value environment, H is treated2O2The method has the advantages that effective catalysis is realized, ferric hydroxide precipitates are easy to produce in a neutral environment, so that the catalyst is inactivated, therefore, an acid adjusting pool is required to be arranged at the front end of the conventional homogeneous Fenton process, a neutralizing pool is arranged at the rear end of the conventional homogeneous Fenton process, a large amount of acid and alkali are consumed in the treatment process, the operation cost is high, and the environmental pollution is easy to cause. The heterogeneous Fenton process is not as efficient as the homogeneous Fenton process, but has wider pH applicability and good application prospect.
From the existing literature data, the traditional method for preparing the nano magnetite adopts a coprecipitation method, and the surface activity of the catalyst is influenced and the catalytic performance is not high due to the poor crystallinity and particle size uniformity of the nano magnetite synthesized by the coprecipitation method. The existing hydrothermal synthesis method has many advantages, does not need calcination and ball milling, has good application prospect, but has the problem of long reaction period, and the growth process is difficult to observe and control because the hydrothermal synthesis method is carried out in a closed container in the synthesis process, so if a ferromagnetic heterogeneous catalyst can be prepared by optimizing the hydrothermal synthesis method, H can be efficiently decomposed2O2The method can prevent the loss of the catalyst from causing secondary pollution while generating hydroxyl free radicals, and has practical application value.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a spherical nano magnetite heterogeneous Fenton catalyst, which comprises the following steps:
s1, mixing ferric iron and ferrous iron, dissolving in distilled water, wherein the molar ratio of ferric iron to ferrous iron is controlled to be 2: 1-4: 1, introducing nitrogen in the dissolving process, and stirring and reacting for 15-30 min to form a solution for later use;
s2, adding a surface coupling agent into the S1 treatment solution, controlling the concentration ratio to be 20-40 g/L, and fully stirring until the surface coupling agent is completely dissolved to form a solution for later use;
s3, slowly adding ammonia water into the solution treated by the S2 under the nitrogen condition, controlling the volume ratio of the ammonia water to the solution treated by the S2 to be 100-200 mL/L, and mechanically stirring for 10-30 min;
s4, after ammonia water is dripped, adding 80 wt% hydrazine hydrate, wherein the adding amount of the hydrazine hydrate is 50-100 mL/L, uniformly mixing to form a suspension, uniformly dispersing for 5-15 min by low-frequency ultrasound, then transferring the solution system into a hydrothermal kettle, reacting for 8-10 h at a constant temperature of 160-180 ℃, cooling to room temperature, adding polyethylene glycol, wherein the adding amount of the polyethylene glycol is 5-20 mL/L, uniformly mixing to form a suspension, uniformly dispersing for 5-15 min by low-frequency ultrasound, and then transferring the solution system into a microwave reactor for catalytic reaction for 30-60 min;
s5, cooling to room temperature after the reaction is finished, performing solid-liquid separation by using a magnetic separation method, alternately washing the separated and synthesized product by using deionized water and absolute ethyl alcohol until the pH value of the supernatant is neutral, collecting black solids, performing vacuum freeze drying at-80 ℃ for 24-30 h, grinding, crushing and sieving to obtain the nano Fe3O4And obtaining the novel spherical nano magnetite heterogeneous Fenton catalyst.
In the step S1, the ferric iron is FeCl3·6H2O or ferric sulfate Fe2(SO4)3·xH2O, ferrous iron is FeCl2·6H2O or ferrous sulfate FeSO4·4H2O。
In the step S2, the surface coupling agent is a silane coupling agent, a borate coupling agent, a titanate coupling agent, or polyvinylpyrrolidone (PVP). The coupling agent is mainly used for improving the interface action of the catalyst, and can improve the interface bonding force of internal molecules of the catalyst and improve the thermal stability.
In the step S4, the frequency of the low-frequency ultrasound is 20 to 40kHz, and the sound energy density is controlled to be 300 to 500W/m3(ii) a The microwave reaction working power is 400-600W, and the reaction temperature is controlled to be 100 ℃.
In the step S4, the polyethylene glycol is polyethylene glycol 200, polyethylene glycol 600 or polyethylene glycol 1000.
The second purpose of the invention is to provide a novel spherical nano magnetite heterogeneous Fenton catalyst prepared by the preparation method. The particle size of the catalyst is 40-150 nm.
The third purpose of the invention is to provide the application of the novel spherical nano magnetite heterogeneous Fenton catalyst in heterogeneous Fenton method water treatment. Preferably, the method is applied to the heterogeneous Fenton pretreatment or advanced treatment of industrial wastewater and landfill leachate.
The invention has the beneficial effects that:
(1) compared with the traditional coprecipitation method, the preparation process of the catalyst is simple, the pH value and the temperature of the system reaction do not need to be finely regulated, and the catalyst is suitable for large-scale production.
(2) Compared with the existing heating synthesis technology, the microwave-assisted hydrothermal synthesis method is adopted, the advantages of the two heating methods are combined, on the basis of the advantages of no sintering, low production cost and the like of the hydrothermal method, the microwave is assisted, heat is generated through high-frequency oscillation friction among molecules, the treatment time of the hydrothermal method is shortened, and the synthesized catalyst is more uniform.
(3) The spherical nano magnetite prepared by the method has ferromagnetism, is easy to recycle, is environment-friendly, and has stronger application prospect and market value.
(4) Compared with the conventional homogeneous Fenton process, the heterogeneous Fenton process has the advantages that the COD treatment efficiency of the wastewater is reduced, but acid and alkali regulation units are reduced because acid and alkali regulation is not needed, the catalyst loss is reduced, the investment and operation cost is reduced, and the cost is obviously saved.
(5) Compared with the commercially available nano magnetite catalyst with smaller particle size, the catalyst prepared by the invention has relatively larger particle size, and the performance of the catalyst is slightly lower than that of the commercially available nano magnetite in the early stage of use, but on one hand, the catalyst prepared by the invention has higher recovery amount and catalytic efficiency in the later stage of use than those of the commercially available nano magnetite under the condition of no catalyst supplement due to larger particle size and stronger magnetism, so that the catalyst prepared by the invention can reduce the catalyst supplement amount and frequency under the condition of ensuring that the water quality is discharged after reaching the standard, and has better economic benefit.
Drawings
FIG. 1 is an X-ray diffraction diagram of the novel spherical nano-magnetite heterogeneous Fenton catalyst prepared in example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of the heterogeneous Fenton catalyst with spherical nano-magnetite prepared in example 1 of the present invention.
FIG. 3 is a room temperature magnetic hysteresis diagram of the novel spherical nano-magnetite heterogeneous Fenton catalyst prepared in example 1 of the present invention.
FIG. 4 is a process flow diagram of example 1 of the present invention. In fig. 4: 1. inlet pipe, 2, H2O2The device comprises a water inlet pipe, 3, a water flow distributor, 4, a catalyst preparation device of the invention, 5, a baffle, 6, a magnetic separator, 7, a catalyst return pipe, 8 and a water outlet pipe.
Detailed Description
The present invention will be better understood by those skilled in the art from the following examples. The examples are described only to illustrate the invention and should not be construed as limiting the invention as detailed in the claims. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
A preparation method of a novel spherical nano magnetite heterogeneous Fenton catalyst comprises the following steps:
firstly FeCl3·6H2O and ferrous chloride FeCl2·4H2Dissolving O in distilled water, wherein Fe3+With Fe2+The molar ratio is controlled to be 2:1 in order to avoid Fe in the solution2+Oxidizing, introducing nitrogen in the dissolving process, and stirring for reacting for 15min to form a solution for later use; then adding polyvinylpyrrolidone (PVP) with the concentration ratio controlled at 20g/L, and fully stirring until the PVP is completely dissolved; slowly adding ammonia water under the condition of nitrogen, controlling the volume ratio of the ammonia water to the solution at 200mL/L, and mechanically stirring for 10min in the adding process; after the ammonia water is added, hydrazine hydrate (N) with the content of 80 wt% is added2H4·H2O), controlling the adding amount of hydrazine hydrate to be 50mL/L, uniformly mixing to form a suspension, uniformly dispersing for 15min by adopting 20kHz low-frequency ultrasonic, and controlling the sound energy density to be 300W/m3Transferring the treated solution into a hydrothermal kettle, and reacting at the constant temperature of 180 ℃ for 10 hours; cooling to room temperature, adding polyethylene glycol 600 with the addition of 5mL/L, mixing to obtain suspension, dispersing with 20kHz low frequency ultrasound for 15min, and controlling sound energy density to 300W/m3Then transferring the solution system to a microwave reactor for catalytic reaction, wherein the working power is 600W, the reaction temperature is controlled to be 100 ℃, and the reaction time is 30 min; cooling to room temperature after the reaction is finished, performing solid-liquid separation by using a magnetic separation method, alternately washing the separated and synthesized product with deionized water and absolute ethyl alcohol for a plurality of times until the pH value of the supernatant is neutral, collecting black solids, then performing vacuum freeze drying at-80 ℃ for 24h, grinding, crushing and sieving to obtain the nano Fe3O4And obtaining the novel spherical nano magnetite heterogeneous Fenton catalyst, wherein the particle size of the catalyst is 40-150 nm. Further, the catalyst is analyzed by XRD (fig. 1), scanning electron microscope (fig. 2) and magnetic performance (fig. 3), and the synthesized spherical nano magnetite heterogeneous fenton catalyst has a spinel structure, good crystallinity and dispersibility, a spherical shape, and ferromagnetic behavior.
The preparation process flow of the novel spherical nano magnetite heterogeneous Fenton catalyst is shown in figure 4.
Example 2
A preparation method of a novel spherical nano magnetite heterogeneous Fenton catalyst comprises the following steps:
firstly FeCl3·6H2O and ferrous chloride FeCl2·4H2Dissolving O in distilled water, wherein Fe3+With Fe2+The molar ratio is controlled to be 2:1 in order to avoid Fe in the solution2+Oxidizing, introducing nitrogen in the dissolving process, and stirring for reacting for 15min to form a solution for later use; then adding a silane coupling agent KH550, controlling the concentration ratio at 15g/L, and fully stirring until the KH550 is completely dissolved; slowly adding ammonia water under the condition of nitrogen, controlling the volume ratio of the ammonia water to the solution at 200mL/L, and mechanically stirring for 10min in the adding process; after the ammonia water is added, hydrazine hydrate (N) with the content of 80 wt% is added2H4·H2O), controlling the adding amount of hydrazine hydrate to be 50mL/L, uniformly mixing to form a suspension, uniformly dispersing for 15min by adopting 20kHz low-frequency ultrasonic, and controlling the sound energy density to be 300W/m3Transferring the treated solution into a hydrothermal kettle, and reacting at the constant temperature of 180 ℃ for 10 hours; cooling to room temperature, adding polyethylene glycol 600 with the addition of 5mL/L, mixing to obtain suspension, dispersing with 20kHz low frequency ultrasound for 15min, and controlling sound energy density to 300W/m3Then transferring the solution system to a microwave reactor for catalytic reaction, wherein the working power is 600W, the reaction temperature is controlled to be 100 ℃, and the reaction time is 30 min; cooling to room temperature after the reaction is finished, performing solid-liquid separation by using a magnetic separation method, alternately washing the separated and synthesized product with deionized water and absolute ethyl alcohol for a plurality of times until the pH value of the supernatant is neutral, collecting black solids, then performing vacuum freeze drying at-80 ℃ for 24h, grinding, crushing and sieving to obtain the nano Fe3O4And obtaining the novel spherical nano magnetite heterogeneous Fenton catalyst, wherein the particle size of the catalyst is 80-120 nm.
Example 3
Firstly Fe2(SO4)3·xH2O and ferrous chloride FeSO4·4H2Dissolving O in distilled water, wherein Fe3+With Fe2 +The molar ratio is controlled to be 4:1 in order to avoid Fe in the solution2+Oxidizing, introducing nitrogen in the dissolving process, and stirring and reacting for 30min to form a solution for later use; then adding polyvinylpyrrolidone (PVP) with the concentration ratio controlled at 40g/L, and fully stirring until the PVP is completely dissolved; slowly adding ammonia water under the condition of nitrogen, controlling the volume ratio of the ammonia water to the solution at 100mL/L, and mechanically stirring for 30min in the adding process; after the ammonia water is added, hydrazine hydrate (N) with the content of 80 wt% is added2H4·H2O), the adding amount of hydrazine hydrate is controlled to be 100mL/L, after the hydrazine hydrate and the hydrazine hydrate are uniformly mixed to form a suspension, the suspension is uniformly dispersed for 5min by adopting 40kHz low-frequency ultrasonic, and the sound energy density is controlled to be 500W/m3Transferring the treated solution into a hydrothermal kettle, and reacting for 8 hours at the constant temperature of 160 ℃; cooling to room temperature, adding polyethylene glycol 200 with the dosage of 20mL/L, mixing to obtain suspension, dispersing with 40kHz low frequency ultrasound for 5min, and controlling the sound energy density to be 500W/m3Then transferring the solution system to a microwave reactor for catalytic reaction, wherein the working power is 400W, the reaction temperature is controlled to be 100 ℃, and the reaction time is 60 min; cooling to room temperature after the reaction is finished, performing solid-liquid separation by using a magnetic separation method, alternately washing the separated and synthesized product with deionized water and absolute ethyl alcohol for a plurality of times until the pH value of the supernatant is neutral, collecting black solids, then performing vacuum freeze drying at-80 ℃ for 30h, grinding, crushing and sieving to obtain the nano Fe3O4And obtaining the novel spherical nano magnetite heterogeneous Fenton catalyst, wherein the particle size of the catalyst is 40-150 nm.
Example 4
The spherical nano magnetite heterogeneous Fenton catalyst prepared in the embodiment 1 is used for constructing a Fenton fluidized tower treatment unit (FBR-Fenton) to carry out advanced treatment on tail water after biochemical treatment of certain printing and dyeing wastewater, and the process flow is as follows: mixing the effluent of the secondary sedimentation tank with hydrogen peroxide, and then feeding the mixture into a Fenton fluidization tower from a bottom pipeline, and feeding the mixture H into a reactor2O2Dosage and waste water CODCrAccording to the mass ratio of 1:1, a novel spherical nano magnetite heterogeneous Fenton catalyst in a Fenton fluidized tower is subjected to mixed reaction, and the mixed reaction is carried outThe adding amount of the novel spherical nano magnetite heterogeneous Fenton catalyst is 150g/L, the catalyst is made to be in a fluidized state through a water flow distributor, the retention time of wastewater is 60min, the wastewater is discharged from the upper part of the tower through downward countercurrent, and the taken catalyst can be recovered through an external magnetic field (magnetic disc) and then flows back to the Fenton fluidized tower.
Meanwhile, compared with the conventional Fenton process, the process flow is as follows: the effluent of the secondary sedimentation tank enters an acid regulating tank and passes through H2SO4Adjusting pH to about 3.0, and introducing into a catalyst mixing tank, and FeSO4·7H2O2The dosage is 95mg/L (Fe)2+0.34mmol/L), and then enters an oxidation reaction tank, and H2O2Dosage and waste water CODCrThe mass ratio of the components is 1:1, the components are uniformly stirred and mixed, and after the reaction is carried out for 60min, the mixture enters a neutralization tank, the pH value is adjusted to about 7.5 by adding NaOH, and then the mixture flows out of a reaction unit.
The results of the processes without and with catalyst and the conventional Fenton process are shown in Table 1.
TABLE 1 comparison of the effects of treating tail water of dyeing wastewater by different processes
According to the experimental results, H alone2O2Since no OH is formed, the oxidation ability is weak and the effect of advanced treatment is poor. After the novel spherical nano magnetite heterogeneous Fenton catalyst prepared in the embodiment 1 of the invention is added, the treatment efficiency is obviously improved, and the COD (chemical oxygen demand) is increasedCrThe average removal rate is 36.3 percent, and the COD of the effluent water is obtained in a part of time periodCrCan meet the requirement of surface water V-class water. Although the treatment efficiency is lower than that of the conventional Fenton process, the acid and alkali regulation unit is reduced and the catalyst loss is reduced due to no need of acid and alkali regulation, the investment and operation cost is reduced, the treatment cost of the conventional Fenton process is 1.5-1.6 yuan/ton, and the treatment cost of the Fenton process taking the catalyst prepared by the method as the core is 1.0-1.1 yuan/ton.
Example 5
A Fenton fluidized tower treatment unit (FBR-Fenton) is constructed by using the spherical nano magnetite heterogeneous Fenton catalyst prepared in the embodiment 2 to carry out advanced treatment on tail water after biochemical treatment of papermaking wastewater, and the process flow refers to the embodiment 4. The results of the treatment effect pairs of the conventional Fenton process (in accordance with the unit of example 4) with no catalyst added and without catalyst added are shown in Table 2.
TABLE 2 comparison of the effects of different processes on treating papermaking wastewater
According to the experimental result, after the novel spherical nano magnetite heterogeneous Fenton catalyst prepared in the embodiment 2 of the invention is added, COD is obtainedCrThe average removal rate is 44.0 percent, and the effluent CODCrCan stably meet the discharge requirement of the discharge standard of water pollutants for pulping and paper making industry (GB 3544-2008). Although the treatment efficiency is lower than that of the conventional Fenton process, the acid and alkali regulation unit is reduced and the catalyst loss is reduced due to no need of acid and alkali regulation, the investment and operation cost is reduced, the treatment cost of the conventional Fenton process is 1.8-2.0 yuan/ton, and the treatment cost of the Fenton process taking the catalyst prepared by the method as the core is 1.2-1.5 yuan/ton.
Example 6
The spherical nano magnetite heterogeneous Fenton catalyst prepared in example 2 is compared with a commercially available nano magnetite catalyst in terms of catalytic performance and catalyst loss rate, and the process flow and the treated wastewater refer to example 4. Through performance measurement, the particle size range of the spherical nano magnetite heterogeneous Fenton catalyst prepared in the embodiment 2 of the invention is 80-120 nm, the saturation magnetization is about 11.9emu/g, the particle size range of the commercially available nano magnetite catalyst is 30-50 nm, and the saturation magnetization is about 7.6 emu/g. According to the results of multiple catalytic degradation experiments (specifically, as shown in table 3), the catalyst prepared in example 2 of the present invention has a relatively large particle size, and although the performance of the catalyst in the early stage of use is slightly lower than that of the commercially available nano magnetite, on one hand, due to the large particle size and the strong magnetism, the catalyst recovery amount and the catalytic efficiency in the later stage of use of the catalyst prepared in example 2 of the present invention are significantly higher than those of the commercially available nano magnetite without the addition of the catalyst due to the baffle plate and the magnetic separation device on the top of the reactor, so that the catalyst prepared in example 2 of the present invention can reduce the catalyst addition amount and frequency and has better economic benefits under the condition of ensuring that the water quality is discharged after reaching the standard.
TABLE 3 COD of different catalystsCrComparison of removal Rate with catalyst recovery
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (9)
1. A preparation method of a novel spherical nano magnetite heterogeneous Fenton catalyst is characterized by comprising the following steps:
s1, mixing ferric iron and ferrous iron, dissolving in distilled water, wherein the molar ratio of ferric iron to ferrous iron is controlled to be 2: 1-4: 1, introducing nitrogen in the dissolving process, and stirring and reacting for 15-30 min to form a solution for later use;
s2, adding a surface coupling agent into the S1 treatment solution, controlling the concentration ratio to be 20-40 g/L, and fully stirring until the surface coupling agent is completely dissolved to form a solution for later use;
s3, slowly adding ammonia water into the solution treated by the S2 under the nitrogen condition, controlling the volume ratio of the ammonia water to the solution treated by the S2 to be 100-200 mL/L, and mechanically stirring for 10-30 min;
s4, after ammonia water is dripped, adding hydrazine hydrate, wherein the adding amount of the hydrazine hydrate is 50-100 mL/L, uniformly mixing to form a suspension, uniformly dispersing for 5-15 min by low-frequency ultrasound, then transferring a solution system into a hydrothermal kettle, reacting for 8-10 h at constant temperature of 160-180 ℃, cooling to room temperature, adding polyethylene glycol, wherein the adding amount of the polyethylene glycol is 5-20 mL/L, uniformly mixing to form a suspension, uniformly dispersing for 5-15 min by low-frequency ultrasound, and then transferring the solution system into a microwave reactor for catalytic reaction for 30-60 min;
s5, cooling to room temperature after the reaction is finished, performing solid-liquid separation by using a magnetic separation method, alternately washing the separated and synthesized product by using deionized water and absolute ethyl alcohol until the pH value of the supernatant is neutral, collecting black solids, and then performing vacuum freeze drying for 24-30 h to obtain the nano Fe3O4Grinding, crushing and sieving to obtain the novel spherical nano magnetite heterogeneous Fenton catalyst.
2. The method according to claim 1, wherein in step S1, the trivalent iron is ferric chloride or ferric sulfate, and the divalent iron is ferrous chloride or ferrous sulfate.
3. The method according to claim 1, wherein in step S2, the surface coupling agent is a silane coupling agent, a borate coupling agent, a titanate coupling agent, or polyvinylpyrrolidone.
4. The method according to claim 1, wherein in step S4, the frequency of the low frequency ultrasound is 20 to 40kHz, and the sound energy density is controlled to be 300 to 500W/m3(ii) a The microwave reaction working power is 400-600W, and the reaction temperature is controlled to be 100 ℃.
5. The method according to claim 1, wherein in step S4, the polyethylene glycol is polyethylene glycol 200, polyethylene glycol 600 or polyethylene glycol 1000.
6. The novel spherical nano magnetite heterogeneous Fenton catalyst prepared by the preparation method according to any one of claims 1 to 5.
7. The novel spherical nano magnetite heterogeneous Fenton catalyst according to claim 6, wherein the particle size of the catalyst is 40-150 nm.
8. The use of the novel heterogeneous Fenton's catalyst of spherical nano-magnetite according to claim 6 or 7 in heterogeneous Fenton's process water treatment.
9. The use according to claim 8, characterized by being used in the pretreatment or advanced treatment of industrial waste water, landfill leachate by the heterogeneous Fenton process.
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